Cell unit for accumulators and method to produce it



Filed July 15 1951 l May 4, T954 D v. WEIL ET AL 2,677,713

CELL UNIT FOR ACCUMULATORS AND METHOD TO PRODUCE IT 2 Sheets-Sheet 1 Ennnnmlfm EDEEDE v. WEIL ET Al. 2,677,713 CELL UNIT FOR ACCUMULATORS AND METHOD TO PRODUCE IT May 4, 1954 2 Sheets-Sheet 2 Filed July 15, 1951 Q7 rra/enfin Werl) @tu www:

Patented May 4, 19544 FUN-ITE S ESS PATENT FICE CELL UNIT FOR ACCUMULATORS AND METHD TO PRODUCE IT Valentin Weil-and WilhelmHeberer, Frankfurt am Main, `Germany The present invention relates to cell units for accumulatore, preferably lead accumulators.

Prior art electrode members or plates used in cell units of lead accumulators, amongst other things, have the most inconvenient `eature of 'being very heavy in relation to their capacity.

A ground therefore results from the fact that a usual 'lead electrode requires a heavy inactive frame-like grid supporting the active paste.

According to the present invention it has been "found and empirically proved that certainarti- 'fic'ial products or plastics are well adapted for the production of positive and negative lectrode members by moulding, forcing or die-casting. Said artificial products or plastics are representatives or derivatesfrom the followingparentsubstances:

(a) Carbon (e. g. .phenol resins); (b) :Watergas (eg. urearesins); (.c) Carbon/lime (e. g. polyvinyl chloride);

.(d) Wood (e. g. viscose);

.(e) Milk (ve...g. casein,.f.orrnaldehyde);

(f) .Silicon (eg. siliccns, varnishvgumsrubber) (g) Boron nitride `compounds (-e.-g..borazol).

All these `parent substances have representatives and derivates which are not aected by dilute and even concentrated sulphuric acid, as well as they are not subjected to oxidation, reduction, or

'Without any diliicultyin x Thus, it is possible to produce gridless or unarmored members A'of high strength and any shape, which are preferably adapted to be used as essentially improved electrode members in accumulators.

With 'the vforegoing in `mimi it is an -important object of the instant invention to provide Anew and useful accumulator `cell units ha-ving 'electrode members enabling the construction of lighter, stabler, and more efficient accumulatore,

especially lead accumulatore.

A further object of the invention `resides in the provisionof acell unit having electrode vmembers which do not requirea framelikeor-armoring grid supporting the .active paste.

Alsoan object of this invention is the provision of an accumulator cell unit having electrode members the vactive layers of Whichrlpartly'convsist :of articial Vbinding products .or plastics which are stable against acids, oxygen, hydrogen, and ozone, and adapted to absorb active paste, such as lead oxide, red lead, iron Apowder o1' nickel powder, to amultiple amount of Vtheir net weight, said 'active layers embracing thin inner current conducting ,portions.

lStill another object 4of the 'Invention isto 'pro- Vide suitable processes 'for producing said new accumulator vcell -units by moulding, forcing ,or die-casting operations with permanent or vtemporary additionrof/suitable substances vso as to control the shape, strength, stability, porosity, and conductivity 'fof electrode members.

While someof the `more salientfeatures, characteristics and advantages 4of 'the instant invention have been abovepointe'd out, others will become vapparent 'from the following disclosures, taken in conjunction with -the accompanying drawings, in which:

Figure 1 is a `perspectivefront view of an accumulator including twelvefplate electrodes, lpartly in section;

Figure 2 is a perspective front View of `an accumulator including six tubular cell units `or pairs of electrodes, partly in section;

Figure 3 is aperspective vside view of a plate electrode produces on themethod in accordance with the invention;

,Figure 4 showsia side 'elevation of a current conductingV grid or intermediate member;

`Figure 5 is ia sidefview of an electrodelayer plate or blanket;

Figure 6 shows a vertical sectional view taken substantially .as indicatedby the line VI-VI of Figure 3;

Figure 7 is a perspective front view `of a plate electrode Vthe lateral klayer plates of which are separated into l'four .rectangular panels;

Figure 8 is a side elevation of a positive plate electrode composedforfour vashlar-like electrode portions;

Figure 9 lis :an-exploded'perspective side view of the plate electrode'illustrated in Figure 8;

Figure L10 isa side elevation of ya current conducting grid or J'intermediate member accumulated with fi-laceous lelectrode portions;

Figure l1 is a side view of a current conducting grid or intermediate member kaccumulated "with both filaceous electrode-portions and lead fibres wherein -said lead VVfibres are fvadapted to 'lead 'the current away-to -a contact iframe;

Figures 12 and-13 are perspective views of different pars of electrodes;

Figure 14 `shows -a ltransversal sectional view .of .an-electrode-fcombinaticn havin-g -a modified shape;

Figure is a perspective View of an electric power accumulating plant constituted by cell units or pairs of electrodes having extensive dimensions;

Figure 16 is a longitudinal section of a cell unit or pair of electrodes shown in Figure 15; and

Figure 17 shows a cross section of the same.

Referring now more specifically to the drawings, in Figure 1 there is shown a container l0 of an accumulator comprising twelve plate electrode members and connecting means I3, I4. Each plate electrode member is constituted by two layer plates or blankets Il, Il' which consist of plastics or artificial products containing suiiicient active paste and which are jointed one to another by pressing operations, thereby embracing a current conducting grid or intermediate member I 2 embedded therein. In Figure 2 there is shown another accumulator container ,i involving six tubular cell units or pairs of electrode members. Each outer tubular electrode member i5 provided with a current conducting grid or intermediate member it is negative and encloses a positive tubular electrode member i5 having a current conducting grid or intermediate member i6. Similar electrode members are connected by Contact bridge pieces i'l and i8, respectively. The plate electrode members shown in Figures 3-6 have a punched or cast current conducting grid or intermediate member i2 provided with meshes 2i. The current conducting grid i2 is enclosed on both sides by layer plates or blankets Il and H by means of a pressing operation. it indicates an upper contact bridge piece having a contact lug I9'. In order to compensate the change of volume of the active paste during charging and discharging the positive plate Aelectrode.member shown in Figure 7 is separated into four panels 22 by joints 23 which are sea-led by a cellular rubber-like substance. 'I'he positive plate electrode member as shown in Figures 8 and 9 comprises four ashlarshaped portions 24 provided with current conducting wires 23. Intermediate layers consist- ,ing of a soft or cellular rubber-like substance are lined between said ashlar-shaped portions 24 being clamped and held together by contact bars 25 and El. The upper bar 2l has a contact lug 2S. The current conducting grid or intermediate member l2 shown in Figure 10 is accumulated with lilaceous electrode particles Sil. In the modiiied embodiment illustrated in Figure i1 said particles Si] are streaked with lead-antimony libres which embody an inner conducting structure. Figure l2 shows a pair of shell-shaped electrode members 32, 32 having inner current conducting grids 39 While Figure 13 illustrates a pair oi' rectangular electrode members 33, 33' provided with inner current conducting grids 3S. In Figure 14 there is shown the cross section oi a pair of electrode members 34, having a special shape so as to. constitute enlarged surfaces Said electrode members 34, 35 are provided with current conducting grids 3l and 35, respectively. Figure 15 shows a power accumulating plant comprising pairs of extensive tubular electrode members or cell units 4i) which may have Welding joints 5i or the like. Connecting means iii-lit connect the electrode members of the cell units di) to negative and positive cables 49, 55, respectively. As shown in Figures 1G and 17, each cell unit comprises an outer negative electrode member including an outer tube 5t, a layer 59, a tubular conducting grid or intermediate member 6i) and a layer 5S', and an inner positive electrode member constituted by a layer S2, a tubular conducting grid 63 and a layer 62. The inner electrode member 62, 63, 62 is provided with passage openings 64. An annular chamber 66 is constituted between the outer electrode member 58, 59, 60, 59 and the inner electrode member 62, 63, 62' which encloses a cylindrical chamber 61. Each cell unit or pair of electrode members is closed at its top by an insulating bonnet 51 carrying pole-terminals 4|, 2. The cell units 40 are mounted upon a big tank 53 containing an electrolyte. A pump 55 which is actuated by a motor moves the electrolyte through a pipe system 54 into the cylindrical chamber 61, then through the passage openings 64 of the inner electrode member 62, 63, 62 into the annular chamber 6E, thus penetrating the outer porous electrode member 58, 59, G, 59 up to its outer jacket tube 58. The electrolyte is sucked from the chamber 65 through a pipe system 52 back to the tank 53 so that the circuit is closed and the cyclic motion can be continued. With the power accumulating plant described it is possible to accumulate very great capacities. If the outer jacket tubes 58 are stable against external influences, such plants may be erected in the open air.

Carbon, water gas, carbon/lime, Wood, milk, silicon, boron nitride compounds have certain derivates such as for example phenol resins, urea resins, polyvinyl chloride, viscose, casein, formaldehyde, silicons, varnish gums, rubber, borazol, respectively, which are stable against acids, even concentrated sulfuric acid, oxygen, hydrogen and adapted to absorb active pastes, such as for example lead dust, litharge, red lead of the like, up to the tenfold amount of their net weight without unfavourably iniiuencing the processing. Thus, in contrast to prior art active pastes which require a special supporting frame or grid, it is possible to make stable paste layers or bodies of high strength and various shape, such as i'or example plates, prole pieces, tubes, laceous members or the like, so as to enable the manufacture of accumulator cell units and electrode members of different kinds. The porosity of such electrode members can be controlled by adding substances, such as for example sodium carbonate, starch, tetrahydrofurane or the like, which will be removed later by boiling or rinsing operations or the like. But it is also possible to influence the degree of porosity by inserting horsehair layers which are carbonized due to heating arising during the pressing operation and rinsed by the acid. The electrical conductivity of such active pastes can be increased by inserting long ribred or small cut lead, lead-antimony compound or leaded mineral fibres or by adding very small quantities of colloidal graphite.

The process according to the present invention for example consists in adding certain colloids or colloid-like substances, such as for example gelatin, casein, methyl cellulose, acetates, to the active paste used such as lead powder, lead oxide, nickel powder, iron powder, so as to constitute electrode members which will be made insoluble with respect to the electrolyte by means of a hardening liquid such as for example alcohol and solution of formaldehyde.

By the following the process of production with accordance to the invention will be described more specically in the case of using polyvinyl chloride: A mixture consisting of about g.

lead oxide, about 35 g. polyvinyl chloride, about 85 g. sodium carbonate, and 30 g. lead Wool are thoroughly homogenized by means or" a ball mill. The paste obtained will be pressed under a pressure of about 500 kg. per dm.2 and a temperature of about 170 C. so as to constitute quadratic layers or blanket having dimensions 13 X 13 x 0.6 cm. Then a current conducting member which is preferably a cast or punched lead or lead-antimony plate having a suilicient number of meshes is located intermediate two of said layers or blankets the adjacent surfaces of which having been previously provided with a thin coating of polyvinyl chloride. Now pressure and heat to the same amount as mentioned above are applied to so as to produce an electrode member. In order to obtain the desired degree of `porosity the sodium carbonate is removed by a rinsing operation with hot Water. The electrode member may be provided with any number` of through holes to increase the perviousness as to the electrolyte.

For the purpose of producing an electrode member of greater porosity, for example the electrode of a starter battery, a polyvinyl chloride paste containing a possibly small amount of a plasticizer is homogeneously kneaded with active paste, such as lead oxide or the like, of the eightfold quantity of the net weight of polyvinyl chloride. Then this mixture is embedded into a mould, into which is inserted a suitable current conducting member, and subjected to a heating operation under a temperature of about 160 C., thus jelling to a cellular rubber-like substance. The cooling process having to take place in the mould will solidify the paste. The plasticizer thereafter has to be lixiviated by means o1" a hot acid to avoid the formation of other acids during the subsequent electro-chemical process. lf the plate electrode is separated into several panels the joints are sealed with a porous rubberlike compound which is adapted to be penetrated by the electrolyte. Cell units or pairs of electrode members of any shape `which can be produced by moulding, forcing or die-casting can be connected to greater units by a Welding or similar operation.

Although for example polyvinyl chloride generally does not conduct electric current it has been surprisingly found that if being located in an electrolyte electrodes produced by means of said substance Will not impair the ionic migration. .it is suggested that the electrolyte solvatizes the artrdcial product particles binding the active particles. A portion of sulphuric acid (about 0.5 per cent), as it were, penetrates into the artificial substance acting therein as a kind of plasticizer which makes the articial substance porous. Moreover, as the attractive force between electropositive and negative ions is considerable the ionic migration arising during the electro-chemical process is enabled to develop Without any difnculty.

This perception will be very important and even revolutionary for the whole accumulator industry as the process described enables to produce electrodes life and capacity of which is increased While their Weight and quantity of lead required is decreased due to the omission of the usual grid frame supporting the active paste.

The manner of using and applying the illustrative embodiments of our invention set forth above as Well as the process described will be clear from the foregoing description. It is, of course, to be understood that our invention is not limited to the specific embodiments here shown and described for purposes of illustration only.

.Various changes and modications may be made d in the accumulator cell unit and the method of its production set forth and in the structural details shown, Without departing from the spirit and the leading ideas of this invention.

We claim:

l. A substantially self-supporting electrode for accumulators, especially of the lead type, which comprises a substantially self-supporting shaped electrode body having an electric conductor embedded therein and predominantly composed of a composition including a substantially acid, oxygen-, hydrogen-, and ozone-resistant plastic substantially traversable for ion migration in an accumulator electrolyte and carrying dispersed throughout its mass a multiple of electrolyte responsive accumulator material by Weight of plastic present, said composition having been heated to a temperature of at least incipient fusion.

2. Electrode in accordance With claim 1 in which said plastic is a member of the group consisting of polyethylene, polystyrol, polyamide, phenol resin, polyester, silicone resin, polyurethane, and polymonochlortriuorethylene.

3. Electrode according to claim 2 in which said plastic is a thermoplastic and in which said electrolyte responsive accumulator material is of the lead compound type.

4. Method for producing a substantially selfsupporting electrode for accumulatore, especially of the lead type which comprises intimately mixing a normally heat fusible acid, oXygen-, hydrogenand ozone-resistant plastic in substantially subdivided form With a multiple of its Weight or" substantially subdivided electrolyte responsive accumulator material, and heating the resulting composite to a temperature of at least incipient fusion.

5. Method according to claim 4 in which said plastic is admixed in the form of a substantially aqueous dispersion.

6. Method according to claim 4 in which said plastic is admixed in the form of a substantially aqueous emulsion of its solution in a substantially organic solvent.

7. Electrode according to claim 1, in which said plastic is thermo-plastic polyethylene.

8. Method according to claim 4, in which a substantially water-soluble, finely divided material is additionally mixed With said plastic, and which includes removing said nnely divided material after said fusion by Washing.

9. Method according to claim 4, which includes additionally mixing with said plastic a material which will carbonite at the temperature of said heating.

References Cited in the iile of this patent UNITED STATES PATENTS Number `Name Date 645,978 Silvey Mar. 27, 1900 664,679 Renaud Dec. 25, 1900 815,628 Opperman Mar. 20, 1906 913,898 Jonas Mar. 2, 1909 960,115 Salom May 3l, 1910 995,162 Lawrence June 13, 1911 2,030,717 Reinhardt Feb. 11, 1936 2,177,062 Gibbons Oct. 24, 1939 2,514,415 Rasch July l1, 1950 FOREIGN PATENTS Number Country Date 20,596 Great Britain Apr. 13, 1895 of 1894 

1. A SUBSTANTIALLY SELF-SUPPORTING ELECTRODE FOR ACCUMULATORS, ESPECIALLY OF THE LEAD TYPE, WHICH COMPRISES A SUBSTANTIALLY SELF-SUPPORTING SHAPED ELECTRODE BODY HAVING AN ELECTRIC CONDUCTOR EMBEDDED THEREIN AND PREDOMINANTLY COMPOSED OF A COMPOSITION INCLUDING A SUBSTANTIALLY ACID-, OXYGEN-, HYDROGEN-, AND OZONE-RESISTANT PLASTIC SUBSTANTIALLY TRAVERSABLE FOR ION MIGRATION IN AN ACCUMULATOR ELECTROLYTE AND CARRYING DISPERSED THROUGHOUT ITS MASS A MULTIPLE OF ELECTROLYTE RESPONSIVE ACCUMULATOR MATERIAL BY WEIGHT OF PLASTIC PRESENT, SAID COMPOSITION HAVING BEEN HEATED TO A TEMPERATURE OF AT LEAST INCIPIENT FUSION. 